Dyestuff intermediates of the anthraquinone series



Patented Nov. 17, 1953 UNITED STATE,

DYESTUFF INTERMEDIATES OF THE ANTHRAQUINONE SERIES Albin Peter and Erhard Wydler, Basel, Switzerland N Drawing. Application December 3, 1951, Serial No. 259,696

Claims priority, application Switzerland December 8, 1950 12 Claims. (01. 260-374) The present invention relates to dyestufi intermediates of the anthraquinone series.

It has been found that new dyestuff 1ntermediates of the anthraquinone series of the composition:

SOsCl wherein each X stands for a hydrogen, chlorine or bromine atom, and wherein the benzene nuclei I may be further substituted by lower alkyl, lower alkoxy, phenoxy, lower alkyl phenoxy, or halogeno phenoxy groups or halogen atoms, are obtained by the action of ohlorosulfonic acid on the corresponding 1,4-diarylaminoanthraquinone derivative of the composition.

r-@ X i 3 wherein X has the precedingly-recited significance and benzene nuclei I may be unsubstituted or may be substituted as precedingly-indicated and/or may be sulfonated, until the resultant compounds have become soluble in hot dilute alkali metal hydroxide solution, but are still insoluble in water.

Chlorosulfonic acid has heretofore been employed for the sulfonation of arylaminoanthraquinones. However, the products obtained according to the present invention are not sulfonic acids. They are not water soluble; since they contain sulfur and replaceable chlorine, it is clear that they are sulfochlorides. 7

Suitable initial 1,4-diarylaminoanthraquinones for the purposes of the present invention comprise the following: diarylaminoanthraquinones obtained by the condensation of e. g. 1,4-dihydroxyanthraquinone or its leuco compound with aromatic amines, such for example as aminobenzene, the methyl-aminobenzenes, the chloroaminobenzenes, 2 methoxy 1 aminobenzene, 4-methoxy-l-aminobenzene, 4-ethoxy-l-aminobenzene, 5-methyl-2-methoxy-l-aminobenzene, 4 n butyl l aminobenzene, 2,4 dimethyl l-aminobenzene, 2,5-dimethyl-l-aminobenzene, 2,6-dimethyl-1-aminobenzene, 2,4,6-trimethyl-laminobenzene, 6-ethy1-2,4-dimethyl-l-aminobenzene, 2,4,6-triethyll-aminobenzene, 2,3,l,6- tetramethyl-l-aminobenzene, 2-(4-chlorophenoxy) -l-aminobenzene, -phenoxy-l-aminobenzene, 4 (4 chlorophenoxy) 1 aminobenzene, eta; 1,4-diarylamino-6-ohloroand -6-bromoanthraquinones obtained for example by the condensation of the corresponding dihydroxy-halogeno-anthraquinones with aromatic amines, such for example as 4-methyl-l-aminobenzene, 2,6- dimethyl l aminobenzene, 2,4,6 trimethyl l-aminobenzene, etc.; IA-diarylamino-fifl-dichloroanthraquinones such for example as 1,4- di (2,6' dimethyl) phenylamino 6,7 di chloro anthraquinone, 1,4 di (23426 tri methylor -triethyl)-phenylamino-6,7-dichloroanthraquinone, etc., as Well as the sulfonic acids obtained by the action of concentrated and fuming sulfuric acid on the afore-enumerated arylaminoanthraqumones.

In order to prepare the dyestufi intermediates according to the present invention, the starting material is added, while stirring at a temperature between --10 C. and C., to chlorosulfonic acid and the stirring continued within the said temperature range until a test specimen is found to be insoluble in water but soluble in hot dilute alkali metal hydroxide solution.

The reaction product is then poured onto ice or onto a mixture of ice and water or salt water, and the formed precipitate filtered off and washed with water or salt water (aqueous sodium ch10 ride solution). The product may be used as a moist paste, but if desired it may be dehydrated by careful drying, preferably under reduced pressure and at a low temperature, for example room temperature (about 20 C.).

The new intermediates of the present invention can be condensed with amines to provide valuable compounds which are useful as lacquer dyestuffs, pigment dyestuffs and also as dyestuffs for textile fibers. a

The following examples set forth representative exemplary embodiments of the invention, and these examples are intended to be solely illustrative and not at all limitative. In these examples, the parts and percentages are by weight and the temperatures are expressed in degrees centigrade.

Example 1 220 parts of chlorosulfonic acid are preheated to 40. Thereupon, while stirring thoroughly, 23.7 parts of 1,4-di-(2,4',6'-trimethyl)-phenylamino-anthraquinone are introduced into the chlorosulfonic acid Within a period of 2 hours. Stirring is continued at the same temperature until a test specimen is completely-soluble in boiling aqueous sodium hydroxide solution of'2-'% strength, but remains undissolved when stirred in cold water. This condition is attained in about 2 hours. 7

The reaction mass is then poured as aithin stream into a powerfully stirred mixture of "1500 parts of ice and 500 parts of aqueous sodium chloride solution of 20% strength. The precipitate is filtered off and washed neutral with ice water.

The product dissolves in benzene with a blue coloration which is more reddish'than that of the starting material; it dissolves in ethylacetate with red-violet coloration. Sulfur determination shows that the starting material has taken up two sulfochloride' groups.

The intermediate corresponds to the composition:

soiol NH cm .5 S0201 CH3 By replacing the '1;4=-di-(2;4',6'-trimethyl)- phenylamino-anthraquinone by the corresponding quantity of 'l,4-di-(6'-ethyl=2,4'-dimethyl-)- phenylamino-anthraquinone and otherwise proceeding in the aforedescribed manner, asimilar 'productof the composition:

, QHs

S OQCI ,ITIH Ha QzHs .N H .0 Ha

LS or Cl C H3 is obtained.

Example "2 22.3 parts of 1,4-di-(2,6'-dimethyl) -phenylamino-anthraquinone are added in small portions during a period of 1 /2 hours to 118parts of chlorosulfonic acid at 50-55". Thereupon stirring is continued for 3 /2 additional hours. At the end of this period, a test specimen is completely-soluble in hot aqueous sodiumihydroxide solution of 2% strength but is ins'o'luble'in cold until the sulfochlorination 'is complete.

\ CH: I I $02 01 NH( 5 Example 3 223 -parts of 1,4-di-(2,4'-dimethyl)phenylamino-anthraquinone are added, in the course oflhour, to1500 parts-of chlorosulfonic acid at 0. The mixtureis then warmed up to 20, stirred for 20 hours at this temperature, and then the reaction brought to completion by stirring for 4 hours at 40. The product corresponds-in solubility to the conditions described in Examples 1 and 2. It is isolated bypouring the reaction mixture into :a stirred mixture of l0,000 parts of ice and 2500 parts of aqueous; potassium chloride solution of 20% strength, followed by suction filtration and Washing toneutrality.

Determination of the sulfurand chlorine content of the product agrees with the calculated values for a disulfochloride.

The intermediate thus obtained corresponds to the composition:

CH2 I $0201 0 NE on;

C Ha

I SiOzCl CH3 Ewample4 176 parts of chlorosulfoniczacid are cooled to methyl)'phenylamino-anthraquinone are added in small portions-within-a period of .45 minutes. After removal from the cooling bath, the mixture is "warmed to-20 in about-one hour; stirring is continued for 3 more hours at this temperature The mixture is then'poured, while stirring, onto 1000 parts "of finely-divided ice, and the formed precipitate filtered off and washed neutral. Analysis shows the product'to contain 2 sulfochloride groups.

By replacing "the 1,4-.di- ('2,5dimethyl)- phenylamino-anthraquinone by an equivalent quantity of 1,4-di- (2-methoxy-5-methyl) phenylamino anthroquinone and otherwise procleuetding as-aforedescribed, a similar product res s.

The intermediates thus obtained correspond respectively to the compositions:

SOaCl- NH I c m (IJH:

and

l 0 CH3 Example 5 with ice Water.

The intermediate thus obtained is a disulfochloride derivative of the composition:

C2Ht

(I) NH C2Ht NH- C2115 OaCl Cz a Example-,6

5 parts of 1,4-di-(2',3,4',6 tetramethyl)- phenylaminoanthraquinone are introduced at 40' into 45 parts of chlorosulfonic acid. The reaction mixture is stirred for 4 hours at 40, then for 16 hours at 50, and finally for 30 hours at 70. A test specimen will then behave in cold water and in sodium hydroxide solution of 2% strength in the manner indicated in Example 5. The reaction product is isolated by pouring the reaction mixture onto a stirred mixture of 150 parts of ice and 50 parts of aqueous potassium chloride solution of strength, followed bY filtration of the precipitate and Washing of the latter to neutrality with ice-cold water. The precipitate is then dried under reduced pressure at 20. Chlorine determination shows it to be a disulfochlorinated product.

6 s The thus-obtained intermediate corresponds to the composition:

(iJHs CH3 -NH- CH:

Ha SO2C1 CH: S0201 Ha CH:

Example 2' 200 parts of chlorosulfonic acid are preheated to 70, whereupon 26 parts of 1,4-di-(2-chloro)- phenylaminoanthraquinone are stirred in within a period or 2 hours. After stirring has been continued at this temperature for 17 hours, the reaction product is completely soluble in boiling aqueous sodium hydroxide solution of 2% strength. The reaction product does not however dissolve when a test specimen thereof is stirred into cold water. The reaction mixture is poured in the form of a thin stream into a stirred mixture of 1000 parts of ice and 300 parts of water. The separated precipitate is filtered off and washed neutral.

The intermediate thus obtained corresponds to the composition:

Example 8 26 parts of 1,4-di-(4-chloro-)phenylaminoanthraquinone are introduced at -90 into 180 parts of chlorosulfonic acid, and the mixture stirred for 30 hours. The reaction is thereupon complete. Theproduced disulfochlorinated product is isolated by precipitation in a stirred mixture of 800 parts of ice and 200 parts of aqueous potassium chloride solution of 20% strength, followed by filtration and washing to neutrality. Analyses for sulfur and chlorine content correspond to the calculated values. a The thus-obtained intermediate corresponds NH Cl II o NHQC] Example 9 22.5 parts of 1,4-di-(2'-methoxy)-phenylaminoanthraquinone are dissolved at 0-5 in parts of chlorosulfonic acid. Stirring is continued at the aforesaid temperature for 21 hours, and then the reaction product is worked up by pouring the. reaction mass into a stirred mixture 7 of-900 -parts of 1 ice and- 200 parts f wa'ter,i 'fo1- lowed by filtration and washing Ito i neutrality. The test specimen of'the resultant product dissolves completelywhen boiled in an aqueous sodium hydroxide solution of 2% strength, on the other hand, it is insoluble in cold water. Analysis shows that twosulfo-chloride groups have added onto the starting material.

The obtained intermediate corresponds to the composition:

.oom

SOzCl E'zmmple .5 parts of Leadi-(2';4,6-trime'thyl) phenylamino 6 chloro-anthraquinone are stirred for 21 hours at 60 in 28parts of .chlorosulfonicacid. The behavior of a test specimen toward hot aqueous sodium hydroxide solution and toward cold water shows that the reactionhas been completed. The reaction mass is thereupon poured onto a stirred mixture of 120 parts of ice and 50 parts of aqueous sodium chloride solution of strength, and the resultant precipitate is filtered off and washed neutral with ice water.

The resultant intermediate corresponds to the composition:

tee-Adm Example? 2 27.2 parts of 1,4-di-(2',4,6-trimethyl) -phenylamino-6,7-dichloro-anthraquinone are introduced within a period of 1 /2 hoursand at a temperature of 40 into 210 parts of chlorosulfonic acid, stirring is continued. for 4 /2 'additionalhours, and then the reaction mixture is poured onto 1330 parts of crushed-ice. The separated precipitate is filtered off with suction arid is washed neutral. The addition of'2 sulfochloride groups onto the starting materialtis demonstrated by analysis.

The sulfochlorination can also be carried out in a mixture of 176 parts of chlorosulfonic acid and 27 parts of o1eum'(25%) at 60 within a period of 20 hours.

The intermediate corresponds to the composition:

(EH3 SIOzCI Example #13 lnto 220;;parts;1of -.chlorosu1fonic :acid' at 0, 25.8 parts of (1;4-di-(:ZQSFdimethyl)ephenylamino- .637edichloroaanthraquinone are added within a period of :45 minutes, .whereafter stirring is continued ifor'dhoursgat 35-40% .A test specimen of vthe..'.reactionproductissnow 'found to be soluble when .:boilefd'.in .iaque'ous :sodium hydroxide 'solution, but insoluble in cold water; .thisiprecipitate cansbe extracted with ethyl :acetate.

The reaction 'massxis then poured :onto .15400 parts of ice, the formed precipitate separated by filtration and washed :neutral.

Instead of 220parts of chlorosulfonic acid, use may be made of a mixture of parts of chlorosulfonic acid "and 50 parts of sulfuric acid monohydrate.

The intermediate'here obtained corresponds to the composition:

-CH3 ,l S0201 to sun II I CH3 -I S0201 .CH:

Example 14 The 1,4-di-(2',4-dimethyl) -phenylamino-6- chloro-anthraquinone may be replaced by an equivalent amount of the 6-bromo analogue, whereby a similar product results.

The thus-prepared intermediates correspond respectively to the compositions:

O 7 CH3 II I O NH --CHa CH3 02C] and CH3 SOzCl NH CH;

CH; solo] Example 15 02m SOQCI 0 NH 01115 II I Cl- )2115 c' NH- o2H5 an, solol Example 16 100 parts of chlorosulfonic acid are preheated to 40, and 10.4 parts of 1,4-di-(4-chloro-2'- methoxy) phenylamino anthraquinone added thereto within a period of 45 minutes. Stirring is continued for 30 additional hours, whereupon a test specimen dissolves completely when boiled in aqueous sodium hydroxide solution of 2% strength. After pouring the reaction mixture onto 700 parts of ice while stirring, the precipitated reaction product is filtered off and washed neutral. I v

10 The thus-obtained intermediate corresponds to the formula:

Example 17 21.4 parts of 1,4-di-[2'-(4"-chloro) -phenoxy]- phenylamino-anthraquinone are introduced at 0 into parts of chlorosulfonic acid. After stirring for 2 hours at the said temperature, a test specimen of th reaction mixture is practically completely soluble in boiling aqueous sodium hydroxide solution of 2% strength. The reaction product undergoes no change in properties, even if subjected to the action of ice-cold chlorosulfonic acid for 20 additional hours. The reaction mixture is poured onto a stirred mixture of 750 parts of ice and 250 parts of aqueous potassium chloride solution of 18% strength. The formed precipitate is then filtered off and washed neutral. Analysis confirms the presence of a disulfochloride.

The intermediatethus corresponds to the composition:

O NH

I O IQ'H SOzCl Example 18 droxide solution of 2% strength. The reaction product corresponds in its behavior to that of Example 1.

The thus produced disulfochloride, corresponding to the composition:

0 NB CH 3 NH- CH3 assays?" l l is recovered by'pouring the reactionmixtureonto a stirred mixture of 150 parts of ice and 50 parts of saturated .aqueous sodium chloride solution, followed by filtering off the. separated precipitate and then washing-the latter withaqueous sodium chloride solution of 10 strength.

Example 19 parts of 1,4 diphenylamino-anthraquinone are added in the course of 35 minutes and at a temperature'of 0-2i tor35 parts of chlorosulfonic acid, and thereupon the temperature in the cooling bath is raised to"20' within 24 hours. Stirringris. thereuponcontinued..for 5.18 hours at. first at. room temperature, (approximately 20) whereby the-product which isainitially completely soluble in. coldv water becomes progressively less.

soluble ,.thereiI-i;v Finally, themass isheated to 40% for one more hour,- whereupon.la.product is, obtainedzwhich is insoluble .iniwater but. which. is.

completely soluble. in. aqueous. sodium hydroxide.

solution: of 2%: strength. Theproductis re,-. covered by pouring the reactionmixtureinto a...

g NEG- Example 20 not is completely? soluble in boiling; aqueous.

sodium hydroxide solution Qfi.'2.% .1 strength.

The product isisolated by pouring thereaction mixture, .while stirring,..ont0-.1000 parts iof. ice and 200aparts. of potassiumxchloride;solution. of 20% strength. The thus precipitated reaction product is: filtered off and 'washed vto neutrality withaqueoussodium .chloride solution of strength.

I The; intermediate which: is thuszobtained 'corresponds to the composition:

SOzCl L CH3 aqueous sodium" chloride Example 21 113 partsof 1,4-di-(4'-methoxy).-phenylaminoanthraquinone' are introduced into 528 parts. of chloro-sulfonic acid at 15-17" in the oourse 'of one hour. The reaction. mixtureris.

stirred for 14 more hours; it is then heated in the course of 1 hour up to 40 and this temperature is maintained-{constant for an additional 1 hours; A-test specimen isthen insoluble in cold water, but dissolves completely when boiled in aqueous sodium hydroxide solution of 2% strength. The reaction mixture is poured, while stirring, onto 1000 parts. of ice and 500 .parts of solution of 25% strength. The. formed precipitate is filtered off and washed withaqueous sodium chloride so lution of 10% strength until neutrality is achieved.

The intermediate corresponds to the composition:

soiol on IFH- it IOOHs d. nn- OCHa SO2C1 ExampZe'ZZ 10 parts of the sodium salt of lA-di-(sulfonic aoid-e' methyl) -phenyl amino anthraquinone, prepared by sulfonation of the corresponding dyestufi base in oleum, are added in the course ofla half ,hourto 35. parts of..chlorosulf.onic acid at..20... The temperature is thenraised to 40 within a;,perio.d of 2.hours and .is..maintained constant ,for.21 hours. tinuedfor 6 more hours at 60, whereupon. the initially water-soluble product becomes waterinsoluble, dissolving only upon being boiled in aqueous. sodiumhydroxide solution of 2% strength.

The reaction product is isolated by pouring the reaction mixture carefully onto a stirred mixture of parts of ice and 40 parts of aque ous sodiumchloride solution of 26% strength, followed by filtration of the precipitate which is thrown down and washingof the latter to neutrality with aqueous sodium chloride solution of 10% strength.

The thus-obtained.intermediate corresponds to the composition:

( IIIH o113 6. NH- om Example 23 10 parts of 1,4-di-(4'-n-butyl)-phenylaminoanthraquinone are added, at 20 and within the course of 1 hour, to 50 parts of chlorosulfonic acid. After further stirring for 15 hours. the

Finally, stirring is con-- mass is heated for 2 more hours to 40. The reaction product is then insoluble in aqueous so-' sition:

soiol c I H- (oHmoHs H O NH- (CH:)a.CHa

I Example 24 5.7 parts of 1,4-di-(4'-phenoxy) -phenylaminoanthraquinone are added in the course of half an hour to 26 parts of chlorosulfonic acid at a temperature of 16-18. After stirring for 1 hour at 19-20", the material is almost completely water soluble. Stirring is continued under the same conditions for 16 more hours, and there is thus obtained a water-insoluble product which, however, is completely soluble upon heating in. aqueous sodium hydroxide solution of 2% strength.

The reaction mixture is poured in the form of a thin stream into a vigorously stirred mixture of 240 parts of ice and 140 parts of sodium chloride solution of 26% strength. The precipitate thus formed is separated by filtration, and is washed neutral with ice-cold aqueous sodium chloride solution of strength.

The thus-obtained intermediate corresponds to the composition:

N -SOnCl O NH Example 6.4 parts of 1,4-di-[4-(4"-chloro) -phenoxy]- phenylamino-anthraquinone are added within hour at 16l8 to 26 parts of chlorosulfonic acid. The mixture is then stirred further at 19-21, whereupon at the end of 1 hour the reaction product is insoluble in cold water, and is diflicultly soluble in boiling aqueous sodium hydroxide solution of 2% strength. After 16 hours stirring at the said temperature, however, the reaction product is insoluble in cold water, but is completely soluble in boiling aqueous sodium hydroxide solution of 2% strength.

14 The product which corresponds to the composition:

is recovered by pouring the reaction mixture onto a mixture of 240 parts of ice and 240 parts of aqueous potassium chloride solution of 20% strength, followed by filtering ofi the formed precipitate and washing the latter with ice-cold aqueous potassium chloride solution of 10% strength.

Example 26 334 parts of a 20% paste of the disulfochloride of Example 1 from 2,4-di-(2,4',6'-trimethyl) phenylamino-anthraquinone are stirred with 180 parts of a 20% solution of the sodium salt of 2- aminoethane-sulfonic acid, the mixture bein maintained for 3 hours at 50 after the addition of 20 parts of sodium bicarbonate and 100 parts of isopropanol The reaction mixture, which has thus become water-soluble, is refluxed for 2 more hours at 80, 80 parts of sodium chloride are added, the mixture stirred cold, filtered, and the thus-isolated acid dyestuff-which dyes wool, silk and nylon in vivid reddish-blue shades of good fastness properties-washed neutral with aqueous sodium chloride solution of 10% strength, and dried.

Having thus disclosed the invention, what is claimed is:

1. A dyestuff intermediate of the anthraquinone series, which corresponds to the formula wherein X stands for an atom selected from the group consisting of hydrogen, chlorine and bromine, and wherein R represents a member selected from the group consisting of hydrogen,

lower alkyl, lower alkoxy, phenoxy, lower alkyl phenoxy, halogeno phenoxy groups and halogen atoms.

2. The dyestufi intermediate of the anthra quinone series corresponding to the formula CH1 SOsCl (f 11TH --CHa NH- -GH:

CH: S OaCI O NH SOaCl CH 4; The dyestuff intermediate of the anthraquinoneseries corresponding to the. formula C2415 SOzCl 5. The dyestuif'intermediate of the. anthraquinone series corresponding to the formula NH- CH3 1H ([3113 slozCl NH CH3 1H: CH3

6. The dyestuff intermediate of the anthraquinone series corresponding; to the formula 7. Aprocess for the manufacture of adyestuff intermediate of the anthraquinone series, com- 16 prisinggthevstep ofrtreating a 1,4-diary1aminoan-thraquinone. corresponding to theaformula R..- wherein X stands foraanz" atom selected from the groupconsisting :of; hydrogen, chlorine and. bromine, and wherein R represents a member selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, henoxy, lower alkyl phenoxy, halogeno phenoxy and sulfonic acid groups and halogen atoms, with chlorosulfonic 20 acid at a temperature between -10" C. and +100 C. in a medium consisting of an excess of said acid.

8. A process for the manufacture of a dyestuif intermediate of theanthraquinone series consist;ng in the step of treating 1,4-di-(2,4,6-

trimethyl) phenylamino anthraquinone with chlorosulfonic acid at a temperature between 10 C. and +100 ,C. in a medium consisting of an excess of said acid.

? 9. A process for the manufacture of a dyestufi intermediate of the anthraquinone series consisting in the step of treating 1,4-di-(2',6- dimethyl) -pheny1amino anthraquinone with chlorosulfonic. acid at. a temperature between 30 10' C. and +-100 C. in a medium consisting of an excess of 'saidacid';

l0; Aprocessfor the manufacture of a dyestuff I intermediate of the anthraquinone series consisting inithe step of treating 1,4-di-(2,4',6'-

49 triethyl) phenylamino anthraquinone with chlorosulfonic acid at a temperature between -10 C. and +100' C. in a medium consisting of an excess of said acid;

11. A process for themanufacture of a dyestuffintermediate of the anthraquinone series consisting in the step of treating lA-di- (2132426 -tetramethy1)-phenylamino anthraquinone with chlorosulfonic acid at a temp-erature between -10 C. and +100 C. in a medium 0 consisting of an excess of said acid.

12. A process for the manufacture of a dyestuff intermediate of the anthraquinone series consisting in the. step. of treating 1,4-(sulfo-4'- methyl)-phenylamino-anthraquinone with chlorosulfonic acid at a temperature between -10 C.

and. +l00 C. in a medium consisting of an excess of said acid.

ALBIN PETER. 6o ERHARD WYDLER.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,121,928 Peter June 28, 1938 2,377,145- Gutzwiller May 29, 1945 

1. A DYESTUFF INTERMEDIATE OF THE ANTHRAQUINONE SERIES, WHICH CORRESPONDS TO THE FORMULA 